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WO1996032358A1 - Materiaux composites ceramiques, intermetalliques ou metallo-ceramiques a sensibilite reduite a la desintegration - Google Patents

Materiaux composites ceramiques, intermetalliques ou metallo-ceramiques a sensibilite reduite a la desintegration Download PDF

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Publication number
WO1996032358A1
WO1996032358A1 PCT/US1995/004417 US9504417W WO9632358A1 WO 1996032358 A1 WO1996032358 A1 WO 1996032358A1 US 9504417 W US9504417 W US 9504417W WO 9632358 A1 WO9632358 A1 WO 9632358A1
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WO
WIPO (PCT)
Prior art keywords
composite
ceramic
compounds
group
composites
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1995/004417
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English (en)
Inventor
Jainagesh A. Sekhar
Ming Fu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Micropyretics Heaters International Inc
Original Assignee
Micropyretics Heaters International Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Micropyretics Heaters International Inc filed Critical Micropyretics Heaters International Inc
Priority to AU22453/95A priority Critical patent/AU2245395A/en
Priority to PCT/US1995/004417 priority patent/WO1996032358A1/fr
Publication of WO1996032358A1 publication Critical patent/WO1996032358A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/58085—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicides
    • C04B35/58092—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicides based on refractory metal silicides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/141—Conductive ceramics, e.g. metal oxides, metal carbides, barium titanate, ferrites, zirconia, vitrous compounds

Definitions

  • the present invention relates in general to ceramic, intermetallic or metal ceramic composites. More specifically, this invention relates to a reduced pest (the term "pest” as used herein connotes mechanical disintegration at temperatures under 1000°C), ceramic, intermetallic or metal ceramic products. Even more specifically, this invention relates to reduced pest ceramic, intermetallic or metal ceramic composites comprising a compound selected from the group consisting of compounds between molybdenum and silicon, tungsten and silicon and mixtures thereof and further comprising at least 2 percent by weight excess added elemental silicon than that required for formation of the compound and added silica.
  • This invention also relates to a reduced pest ceramic, intermetallic or metal ceramic composite comprising ternary compounds and mixtures thereof selected from the group consisting of (ZAI x Si y ), where Z is an element and where x is an integer and y is a whole number.
  • MoSi 2 molybdenum disilicide
  • MoSi 2 has the following properties that make it an ideal metal-ceramic for use in applications such as top glass cooking stoves, which utilize a radiant plate placed under a glass ceramic transparent top with the heating element comprising an electrically heated body, supported by an insulating base: (1 ) The resistivity of MoSi 2 increases with temperature. (2) The resistivity-temperature curve for a MoSi 2 heating element is very steep, with the resistivity ratio at 20°C to 1500°C, being about 10.
  • MoSi 2 include abrasives, cutting tools, polishing powders; elements for resistance heating furnaces; high temperature lubricants; neutron alternators; shape-memory alloys; steel melting additives; electrodes for electrolysis of corrosive media; ceramic filters used for filtering undesirable particles from a molten metal before the metal is poured into a pattern or mold; porous ceramic articles used as substrates for catalysts, for removal of contaminants from exhaust gases, for collecting impurities from highly corrosive acids and chemicals; in kiln furniture; aerospace applications; and in structural materials in low density load bearing structures.
  • MoSi 2 and MoSi 2 -containing ceramic or metal ceramic composites also referred to as "pest” continues to be a problem, especially in non-dense (porous), MoSi 2 containing ceramic or metal ceramic composites.
  • MoSi 2 -containing ceramic or metal ceramic composites which are not susceptible to pest formation.
  • USP 4,704,372 to Watanabe et al. relates to a high-strength molybdenum silicide-based ceramic material and a process for producing such ceramic material.
  • a powder mixture obtained by adding to titanium carbonitride 0-100% by weight of a specific metal boride compound is added to powder of molybdenum suicide used as base component, and the obtained mixed powder composition is sintered. Both strength and density of molybdenum suicide are said to be increased while maintaining its low-temperature sinterabilit ⁇ . It is recognized in this patent that the sintered body of MoSi 2 alone is low in strength and also extremely brittle at normal temperature, so that the industrial use of MoSi 2 has been limited to electrical resistance heating elements.
  • Co-pending application USSN 07/847,782 provides a novel technique to make electrical heating elements which may be used up to 1900° C. New methods are also provided for manufacturing ceramic composites, which may be used as both electrical heating elements and oxidation resistant materials. There are also provided in the '782 application, compositions for manufacturing the above mentioned ceramic composites and heating elements. The '782 application is incorporated by reference into the present application. While the '782 application provides methods for the manufacture of electrical heating elements and the like, there is no suggestion that this method alone, i.e. micropyretic synthesis would eliminate, reduce or in any way affect pest in MoSi 2 containing composites. In fact, the '782 application does not even mention pest problems in MoSi 2 containing composites. This application is incorporated by reference herein.
  • porosity One way of reducing the likelihood of formation of pest is by reducing the porosity of the composite. Methods of reducing porosity are described in copending applications 08/027,710, 08/085,313 and 08/242,362. However, porosity may be important for certain applications, including use of the composites in filtration and in separation of gas and liquid mixtures.
  • a reduced pest ceramic, intermetallic or metal ceramic composite comprising a compound selected from the group consisting of compounds between molybdenum and silicon, tungsten and silicon and mixtures thereof, the ceramic, intermetallic or metal ceramic composite further comprising: at least 0.5 percent by weight excess added elemental silicon than that required for formation of said compound; and added silica.
  • a reduced pest, ceramic, intermetallic or metal ceramic composite comprising ternary compounds and mixtures thereof selected from the group consisting of (ZAI x Si y ), where Z is an element and where x is an integer and ⁇ is a whole number.
  • Z is selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Mo, W.
  • the composites further comprise quartenary and higher order compounds related to said ternary compounds and alloying additions including dopants and mixtures thereof.
  • a method of reducing pest formation in a ceramic, intermetallic or metal ceramic composite comprising a compound selected from the group consisting of compounds between molybdenum and silicon, tungsten and silicon and mixtures thereof, comprising: adding to said composite, at least 0.5 percent by weight excess elemental silicon than that required for formation of said compound; and adding silica to said composite.
  • a method of reducing pest in ceramic, intermetallic or metal ceramic composites comprising: including in said composite, ternary compounds and mixtures thereof selected from the group consisting of (ZAI x Si y ), where Z is an element where x is an integer and y is a whole number.
  • Z is selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Mo, W.
  • the composites further comprise quartenary and higher order compounds related to said ternary compounds and alloying additions including dopants and mixtures thereof.
  • a method of reducing pest in ceramic, intermetallic or metal ceramic composites by providing a layer, said layer not comprising predominantly of silica.
  • the layer comprises aluminum oxide.
  • Figure 1 is a photomicrograph of a MoAI 2 Si 2 composite according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • micropyretic synthesis as defined in USP 5,188,678 and in copending application serial number 07,847,782, also known as combustion synthesis or CS or self-propagating high temperature synthesis or SHS
  • powder metallurgy is the preferred technique, as it requires no energy input, relatively little labor and allows the entire manufacturing process to be carried in relatively few processing steps.
  • compositions which result in ceramic, intermetallic or metal ceramic composites with reduced susceptibility to pesting are manufactured using the technique disclosed in USSN 07/847,782, but may be manufactured using any of the techniques discussed above and by those techniques disclosed in the patents and patent applications discussed above. It will be understood that neither the compositions nor the methods limit the present invention.
  • ternary compounds selected from the group consisting of (ZAI x Si y ), where Z is an element where x is an integer and y is a whole number, in small amounts to ceramic, intermetallic and metal ceramic composites with a susceptibility to pesting, dramatically reduced or even eliminated the pesting.
  • Z is selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Mo, W.
  • the preferred ternary compound is MoAl x Si y or molybdenum aluminide with silicon. 10 weight percent added MoAl x Si y was sufficient to observe the reduction in pest formation. Greater the ternary compound, better the pest behavior. Thus a pure ternary compound showed no pesting at all.
  • the reactant powders were first dry-mixed in a plastic jar for 30 minutes using a Spex Industries 800 Mixer/Mill. The well mixed powders were then uniaxially pressed in a 1 -inch-diameter stainless steel die to form disk shaped green compacts. Micropyretic synthesis was then conducted. A micrograph of the resulting product is shown in Figure 1. Such products are currently manufactured by MHI and sold under the trademark GPF-21TM. MoAI 2 Si 2 was identified by X-ray diffraction pattern comparison.
  • MoAI 2 Si 2 has a hexagonal (C40-t ⁇ pe) which is different from the body centered tetragonal (C1 1 b-type) crystal of MoSi 2 , for example.
  • MoAI 2 Si 2 was tested for pest formation at 400, 500 and 600°C. Pesting was not detected at all these temperatures.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Matériau composite céramique, intermétallique ou métallo-céramique à sensibilité réduite à la désintégration, qui comprend un composé sélectionné dans le groupe constitué des composés de molybdène et de silicium et de tungstène et de silicium, et d'au moins 0,5 % en poids d'excédent de silicium élémentaire rajouté à ce qui est nécessaire à la formation du composé. L'invention porte également sur un matériau composite céramique, intermétallique ou métallo-céramique à sensibilité réduite à la désintégration, qui comprend des composés ternaires et leurs mélanges sélectionnés dans le groupe constitué de (ZAIxSiy), où Z représente un élément, x un entier relatif et y un nombre entier.
PCT/US1995/004417 1995-04-11 1995-04-11 Materiaux composites ceramiques, intermetalliques ou metallo-ceramiques a sensibilite reduite a la desintegration Ceased WO1996032358A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU22453/95A AU2245395A (en) 1995-04-11 1995-04-11 Ceramic, intermetallic or metal ceramic composites with a re duced susceptibility to pesting
PCT/US1995/004417 WO1996032358A1 (fr) 1995-04-11 1995-04-11 Materiaux composites ceramiques, intermetalliques ou metallo-ceramiques a sensibilite reduite a la desintegration

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1995/004417 WO1996032358A1 (fr) 1995-04-11 1995-04-11 Materiaux composites ceramiques, intermetalliques ou metallo-ceramiques a sensibilite reduite a la desintegration

Publications (1)

Publication Number Publication Date
WO1996032358A1 true WO1996032358A1 (fr) 1996-10-17

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PCT/US1995/004417 Ceased WO1996032358A1 (fr) 1995-04-11 1995-04-11 Materiaux composites ceramiques, intermetalliques ou metallo-ceramiques a sensibilite reduite a la desintegration

Country Status (2)

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AU (1) AU2245395A (fr)
WO (1) WO1996032358A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001089266A1 (fr) * 2000-05-18 2001-11-22 Sandvik Ab Procede permettant d'augmenter la duree de vie d'elements chauffants a basses temperatures
WO2002026657A1 (fr) * 2000-09-29 2002-04-04 Sandvik Ab Procede permettant d'ameliorer la duree de vie d'un element chauffant d'un disiliciure de molybdene a de plus faibles temperatures

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MCKAMEY ET AL.: "A study of pest oxidation in polycrystalline MoSi2", JOURNAL OF MATERIALS RESEARCH, vol. 7, no. 10, October 1992 (1992-10-01), pages 2747 - 2755 *
P.J. MESCHTER: "Low-temperature oxidation of molybdenum disilicide", METALLURGICAL TRANSACTIONS A, vol. 23A, June 1992 (1992-06-01), pages 1763 - 1772 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001089266A1 (fr) * 2000-05-18 2001-11-22 Sandvik Ab Procede permettant d'augmenter la duree de vie d'elements chauffants a basses temperatures
US6707016B2 (en) 2000-05-18 2004-03-16 Sandvik Ab Method of increasing the length of life of heating elements at low temperatures
WO2002026657A1 (fr) * 2000-09-29 2002-04-04 Sandvik Ab Procede permettant d'ameliorer la duree de vie d'un element chauffant d'un disiliciure de molybdene a de plus faibles temperatures
US6919544B2 (en) 2000-09-29 2005-07-19 Sandvik Ab Method to improve the life span of a heating element of a molybdenium disilicide at lower temperatures

Also Published As

Publication number Publication date
AU2245395A (en) 1996-10-30

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